CN113087647B - Preparation method of cysteine - Google Patents
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- CN113087647B CN113087647B CN201911338507.7A CN201911338507A CN113087647B CN 113087647 B CN113087647 B CN 113087647B CN 201911338507 A CN201911338507 A CN 201911338507A CN 113087647 B CN113087647 B CN 113087647B
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Abstract
The invention discloses a preparation method of cysteine. The preparation method comprises the following steps: 1) Adding an electrode solution into an electrode solution storage tank of a bipolar membrane electrodialysis device, adding pure water into an acid chamber storage tank, and adding a cysteine hydrochloride aqueous solution into an alkali chamber storage tank; 2) Switching on a power supply, starting each chamber driving pump to start a circulation loop, applying voltage and current to the membrane stack, changing water when the conductivity in the acid chamber storage tank is 200-396 ms/cm, switching off the power when the conductivity in the alkali chamber is reduced to 0.3-30 ms/cm, and taking out the feed liquid in the alkali chamber; 3) And (3) carrying out post-treatment on the alkali chamber feed liquid. The preparation method of the invention applies the bipolar membrane electrodialysis system to the production of cysteine for the first time, can greatly reduce the content of cysteine chloride ions in the product, saves the cost and is environment-friendly.
Description
Technical Field
The invention relates to a preparation method of cysteine.
Background
L-cysteine is a common amino acid in organisms, is one of non-essential amino acids of human bodies, has the scientific name of 2-amino-3-mercaptopropionic acid and can be mutually converted with cystine. L-cysteine can participate in the intracellular reduction process and the phospholipid metabolism of the liver, can be used as a liver-protecting medicine, is an amino acid antidote, and can also be applied to the field of medicines due to derivatives thereof. In addition, it has whitening and antioxidant effects, and thus is widely used in other fields such as cosmetics. With the increasing demand of L-cysteine, a proper production process is required to improve the production efficiency and quality to meet the demand.
The electrodialysis technology is a separation method developed on the basis of ion exchange method, and is one of membrane separation technology, and its working principle is that anion-cation exchange membranes are alternatively arranged between positive and negative electrodes, and are separated by special partition plates to form two systems of desalination and concentration, and under the action of DC electric field, the selective permeability (its essence is back diffusion) of ion exchange membranes is used to desalinate a part of water, and a part of water is concentrated to separate electrolyte from solution, so that the concentration, desalination, refining and purification processes of solution are realized.
The membranes for electrodialysis are classified into alloy membranes (heterogeneous membranes), homogeneous membranes (anionic and cationic membranes), bipolar membranes, and the like. The bipolar membrane consists of an anion exchange resin layer, a cation exchange resin layer and an intermediate catalytic layer. H between the cathode film and the anode film composite layer under the action of a direct current electric field 2 Dissociation of O into H + And OH - And pass through the male and female membranes, respectively, as H + And OH - Ion source, bipolar membrane, capable of dissociating water directly into H + And OH - So as to realize the cleavage type decomposition of the inorganic salt and prepare the corresponding acid and alkali. Different membranes can be selected to have different compositions of compartments and membrane stacks depending on the application, and thus can be used in different applications. For example, desalination of seawater by electrodialysis devices (see Lipoyi, wangjianyou, concentrated seawater treatment and new development of comprehensive utilization techniques [ J)]Chemical development 2014 (11); sunzhen, chen superman, wangman, non-drinking simple seawater desalination technology and application [ J]Laboratory research and exploration 2011 (6)), not only can obtain high-quality desalted water, but also can obtain recyclable acid and alkali, and meet the requirements of green and environment-friendly processes.
The amino acid molecular structure has both amino group and carboxyl group, and it has different charges at different pH values, so that it can change its migration direction under the action of electric field by regulating the pH value of amino acid solution. There are also documents (see university of great masters academic paper of tai gen of amino acid wastewater treatment by bipolar membrane electrodialysis technology; university of great masters study of fanyi amino acid fermentation broth electrodialysis desalination of fanyi amino acid) reporting the recovery of high-value amino acid by desalting process of amino acid wastewater with electrodialysis device. The application of the electrodialysis technology in the field of amino acid is mainly separation and purification (the application of the electrodialysis technology in amino acid production [ J ] water treatment technology 2011 (11)), and the electrodialysis technology is developed from a simple two-chamber and three-chamber monopolar membrane system to a multi-compartment bipolar membrane electrodialysis system, so that substances are separated under the conditions of normal temperature and no phase change, no pollutant is generated, and the method is a green and environment-friendly process.
The existing preparation method of L-cysteine (see CN 201410258617) is carried out in a conventional kettle type reactor, the heat release is large, the temperature control difficulty is high, the salt content in the product is high, a large amount of pure water or ethanol is additionally used for leaching to control the chloride content, the lower the chloride content in the product is, the higher the leaching solvent consumption is, even if the chloride content in the product can only reach the standard of 400-2000 ppm.
Therefore, the preparation method of cysteine with low cost, more environmental protection and higher product quality is urgently needed in the field.
Disclosure of Invention
The invention aims to overcome the defects that the conventional kettle type reactor is adopted for reaction in the existing cysteine preparation method in the prior art, the heat release is large, the temperature control difficulty is higher, a large amount of pure water or ethanol is additionally used for leaching to control the chloride content due to high salt content in the product, the lower the chloride content in the product is, the higher the leaching solvent consumption is, even if the chloride content in the product can only reach the standard of 400-2000 ppm, and the like, so that the cysteine preparation method is provided. The preparation method of the invention has low cost, is more environment-friendly, and the chloride content of the product meets the standard and has higher quality.
The present invention solves the above-mentioned problems by the following technical means.
The invention adopts a bipolar membrane electrodialysis system with two compartments to produce cysteine, and completely avoids the problems in the production of the conventional acid-base neutralization method in the prior art.
The invention provides a preparation method of cysteine, which comprises the following steps:
1) Adding an electrode solution into an electrode solution storage tank of a bipolar membrane electrodialysis device, adding pure water into an acid chamber storage tank, and adding a cysteine hydrochloride aqueous solution into an alkali chamber storage tank;
2) Switching on a power supply, starting each chamber driving pump to start a circulation loop, applying voltage and current to the membrane stack, changing water when the conductivity in the acid chamber storage tank is 200-396 ms/cm, and switching off when the conductivity in the alkali chamber is reduced to 0.3-30 ms/cm, and taking out the feed liquid in the alkali chamber;
3) Carrying out post-treatment on the alkali chamber feed liquid;
wherein n is 0 or 1.
In the present invention, the bipolar membrane electrodialysis device is conventional in the art. The bipolar membrane electrodialysis device used by the invention can be specifically composed of a membrane stack and a cathode plate, wherein the electrodialysis membrane stack is formed by sequentially overlapping a bipolar membrane, an anion exchange membrane and a cation exchange membrane according to a certain sequence; the cation exchange membrane faces the polar plate, and a polar chamber is formed between the polar plate and the cation exchange membrane; an acid chamber is formed between the anion exchange membrane and the cation exchange membrane, and an alkali chamber is formed between the anion exchange membrane and the bipolar membrane. The polar chamber is communicated with a polar liquid storage tank, the acid chamber and the alkali chamber are respectively communicated with an acid liquid storage tank and an alkali liquid storage tank, and the indoor solutions and the storage tanks are respectively driven by a driving pump to form respective circulation loops. The polar chamber, the acid chamber and the alkali chamber are all provided with conductivity meters, and the conductivity change of the solution in each chamber can be monitored at any time. A bipolar membrane electrodialysis device particularly applicable in the present invention can be shown in fig. 1. Wherein BM represents a bipolar membrane, AM represents an anion exchange membrane, and CM represents a cation exchange membrane.
In the present invention, the source of the aqueous cysteine hydrochloride solution is not particularly limited, and cysteine hydrochloride which is conventionally converted into an aqueous cysteine hydrochloride solution after dissolving in water in the art or a hydrate thereof in a conventional molar ratio is included in the scope of the present invention. Wherein, the cysteine hydrochloride or the hydrate thereof (such as cysteine hydrochloride monohydrate) can be prepared by self or purchased directly according to the related literature report in the field, and the structure is shown as follows.
In the invention, the cysteine in the cysteine hydrochloride aqueous solution can be L-cysteine or D-cysteine, or a mixture of the two, and the mixture is not limited to the mixture ratio of the two; in the present invention, L-cysteine may be mentioned, for example.
In the step 1), the polar aqueous solution can be conventionally used by devices in the field, and can be a conductive strong electrolyte solution, and specifically can be one or more of dilute sulfuric acid, dilute nitric acid, a sodium hydroxide aqueous solution and dilute hydrochloric acid; dilute sulfuric acid, dilute nitric acid, or dilute hydrochloric acid are preferred for the present invention.
In step 1), the mass fraction of the polar aqueous solution can be conventionally used in such apparatuses in the art, and specifically in the present invention, for example, can be 1 to 2%.
The quantity of said polar aqueous solution used in step 1) can be any quantity conventionally used in the art for such devices, provided that the minimum volume required for the piping circulation of the plant is met. Specifically, the amount of the compound may be, for example, 1 to 3L, 1.5 to 2L, or 150L.
In step 1), the molar concentration of the aqueous cysteine salt solution can be determined by the conventional methods in the art, and in the present invention, the molar concentration can be, for example, 1.5 to 1.7mol/L, or 1.63 to 1.68mol/L, such as 1.65mol/L.
In step 2), the voltage can be applied by a conventional device in the field, and specifically, the voltage can be, for example, 24 to 28V, or 220V.
In step 2), the current can be used conventionally in this field, and specifically in the present invention, for example, 21 to 25A, or 125A can be used.
In step 2), the conductivity in the acid chamber storage tank during water change can be 200-390 ms/cm, such as 300ms/cm.
In the step 2), the number of water changes can be conventionally used by such devices in the field, and specifically in the present invention, for example, can be 1 to 6 times, further, for example, 1 to 4 times, further, for example, 1 to 2 times.
In the step 2), the power can be cut off when the conductivity in the alkali chamber is reduced to 0.3-10 ms/cm, or the power can be cut off when the conductivity in the alkali chamber is reduced to 0.3-0.5 ms/cm.
In the step 2), the operation time can be conventionally used by the devices in the field, and specifically in the invention, for example, can be 30 to 80min, further 36 to 65min, further 47 to 55min, or 9 to 10h.
In step 2), the temperature of the membrane stack can be conventionally used in the field of such devices, and specifically in the present invention, for example, 30 to 40 ℃.
In the step 3), the post-treatment can be conventionally used in the field of such reactions, and the method specifically comprises the steps of reduced pressure concentration, low-temperature crystallization, suction filtration and drying.
Wherein, the vacuum concentration means the conventional in the field, the vacuum concentration time and the vacuum concentration temperature do not need to be controlled particularly, and the invention can be, for example, 0.5 to 1 hour at 80 ℃, or 5 to 7 hours at 80 ℃.
Wherein, the low temperature crystallization is the conventional one in the art, and the low temperature crystallization time and the low temperature crystallization temperature do not need to be controlled particularly, and in the invention, for example, the crystallization time and the crystallization temperature can be 0.5h at 10-20 ℃, or 2-3 h at 10-20 ℃.
Wherein, the suction filtration drying means the conventional method in the field, and the suction filtration drying time, the temperature and the pressure are not required to be specially controlled.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the preparation method can directly produce the cysteine by using the cysteine hydrochloride or the cysteine hydrochloride hydrate through the bipolar membrane electrodialysis device, thereby saving the raw material cost;
2. the preparation method reduces the generation of waste water and waste, and is more environment-friendly;
3. the content of chloride ions in the cysteine product obtained by the preparation method can reach the standard of less than 50-200 ppm, the yield of the crude product (the ratio of the obtained cysteine amount to the cysteine hydrochloride or cysteine hydrochloride hydrate serving as the raw material) is 45-58%, and the yield of the crude product cannot be reached by the conventional method;
4. the preparation method of the invention utilizes the electrochemical principle and the electrodialysis technology to separate cysteine and chloride ions, and the chloride ions with negative charges are transferred to the anode through the membrane under the action of the direct current power supply, thereby achieving the separation effect.
Drawings
FIG. 1 is a view showing a bipolar membrane electrodialysis apparatus used in an embodiment of the present invention.
Wherein BM represents a bipolar membrane, AM represents an anion exchange membrane, and CM represents a cation exchange membrane;
a feed liquid circulation loop for an alkali chamber, a feed liquid circulation loop for an acid chamber,
Is a polar solution circulation loop.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
In the following examples of the present invention, unless otherwise specified, the content of chloride ions in the product is determined according to pharmacopeia detection standards, and the product yield in the examples is about 50%, which is a statistical result of multiple experiments. The residue refers to the residue on ignition, and the index and method of detection refer to the detection specified in the Japanese pharmacopoeia.
In the bipolar membrane electrodialysis device applicable to the following examples 1 to 4, bipolar membranes represented by BM and anion exchange membranes represented by AM are repeatedly stacked 10 times; in the bipolar membrane electrodialysis devices of the present invention to which the following examples 5 to 6 were applied, the bipolar membrane represented by BM and the anion exchange membrane represented by AM were repeatedly stacked 50 times.
In the following examples, cysteine hydrochloride monohydrate was used as a raw material, and the product yield was calculated by the following formula:
A％＝m1/m2*100％；
wherein m1 is the mass (g) of cysteine, m2 is the mass (g) of cysteine monohydrate hydrochloride, and the theoretical yield is 69 percent at most.
In the following examples of the present invention, the chloride ion removal rate was calculated by the following formula:
B％＝n1/n2*100％；
wherein n1 is the molar weight of chloride ions in cysteine of the product, and n2 is the molar weight of chloride ions in cysteine monohydrate hydrochloride in the raw material.
The transformation processes involved in the following examples of the invention are shown below:
example 1
1.5L of 1% dilute nitric acid is prepared and added into a polar liquid storage tank of a bipolar membrane electrodialysis device; adding pure water into the storage tank of the acid chamber; weighing 1000g of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the hydrochloride until the molar concentration of the hydrochloride in the pure water is 1.68mol/L, and adding the hydrochloride into an alkali chamber storage tank of a bipolar membrane electrodialysis device;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 28V voltage and 25A current to the membrane stack, controlling the temperature of the membrane stack to be 30-40 ℃, changing water for 2 times when the conductivity of hydrochloric acid in the acid chamber storage tank is 390ms/cm, switching off power when the conductivity of the alkali chamber is reduced to 0.3ms/cm, and operating for 55min;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 0.5-1h, crystallizing at 10-20 ℃ for 0.5h, and performing suction filtration and drying to obtain 500g of product, wherein the content of cysteine chloride ion is 50 ppm-200 ppm, the chloride ion removal rate is 99.9%, and the product yield is 50%.
Example 2
1.5L of 1 percent dilute sulfuric acid is prepared and added into an electrodialytic equipment polar liquid storage tank; adding pure water into the acid chamber storage tank; weighing 1000g of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the hydrochloride until the molar concentration of the hydrochloride in the pure water is 1.65mol/L, and adding the hydrochloride into an alkali chamber storage tank of electrodialysis equipment;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 24V voltage and 21A current to the membrane stack, changing water for 1 time when the conductivity of hydrochloric acid in the acid chamber storage tank is 300ms/cm, switching off power when the conductivity of the alkali chamber is reduced to 10ms/cm, and operating for 65min;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 0.5-1h, crystallizing at 10-20 ℃ for 0.5h, and performing suction filtration and drying to obtain 500g of product, wherein the content of cysteine chloride ion is 200 ppm-400 ppm, the chloride ion removal rate is 99.8%, and the product yield is 48%.
Example 3
1.5L of 1% dilute sulfuric acid is prepared and added into an electrodialysis equipment polar liquid storage tank; adding pure water into the acid chamber storage tank; weighing 1000g of DL-cysteine monohydrate hydrochloride, adding pure water to dissolve the DL-cysteine monohydrate hydrochloride until the molar concentration of the DL-cysteine monohydrate hydrochloride in the pure water is 1.5mol/L, and adding the DL-cysteine monohydrate hydrochloride into an alkali chamber storage tank of electrodialysis equipment;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 24V voltage and 21A current to the membrane stack, changing water for 2 times when the conductivity of hydrochloric acid in the acid chamber storage tank is 200ms/cm, switching off power when the conductivity in the alkali chamber is reduced to 0.5ms/cm, and operating for 36min;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 0.5-1h, crystallizing at 10-20 ℃ for 0.5h, and filtering and drying to obtain 450g of product, wherein the chloride ion removal rate is 99.5%, the DL-cysteine chloride ion content is less than 200ppm, and the product yield is 45%.
Example 4
1.5L of 1% dilute sulfuric acid is prepared and added into an electrodialysis equipment polar liquid storage tank; adding pure water into the storage tank of the acid chamber; weighing 1000g of D-cysteine monohydrate hydrochloride, adding pure water to dissolve the D-cysteine monohydrate hydrochloride until the molar concentration of the D-cysteine monohydrate hydrochloride in the pure water is 1.5mol/L, and adding the D-cysteine monohydrate hydrochloride into an alkali chamber storage tank of electrodialysis equipment;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 24V voltage and 21A current to the membrane stack, changing water for 2 times when the conductivity of hydrochloric acid in the acid chamber storage tank is 200ms/cm, switching off power when the conductivity in the alkali chamber is reduced to 0.5ms/cm, and operating for 47min;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 0.5-1h, crystallizing at 10-20 ℃ for 0.5h, and performing suction filtration and drying to obtain 480g of product, wherein the content of D-cysteine chloride ion is less than 200ppm, the chloride ion removal rate is 99.3%, and the product yield is 48%.
Example 5
150L of 1% dilute sulfuric acid is prepared and added into a polar liquid storage tank of a bipolar membrane electrodialysis device; adding pure water into the storage tank of the acid chamber; weighing 500kg of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the L-cysteine monohydrate hydrochloride into the pure water until the molar concentration of the L-cysteine monohydrate hydrochloride in the pure water is 1.63mol/L, and adding the L-cysteine monohydrate hydrochloride into an alkali chamber storage tank of a bipolar membrane electrodialysis device;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 220V voltage and 125A current to the membrane stack, controlling the temperature of the membrane stack to be 30-40 ℃, changing water for 2 times when the conductivity of hydrochloric acid in the storage tank of the acid chamber is 390ms/cm, switching off the power when the conductivity of hydrochloric acid in the alkali chamber is reduced to 0.3ms/cm, and operating for 9 hours;
taking out the feed liquid, carrying out reduced pressure concentration at 80 ℃ for 5-7h, carrying out low temperature crystallization at 10-20 ℃ for 2-3 h, carrying out suction filtration and drying to obtain 241g of product, wherein the content of cysteine chloride ion is 50-200 ppm, the removal rate of chloride ion is 99.9%, and the yield of product is 46.2%.
Example 6
Preparing 150L of 1% dilute sulfuric acid, and adding the dilute sulfuric acid into a polar liquid storage tank of a bipolar membrane electrodialysis device; adding pure water into the acid chamber storage tank; weighing 525kg of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the hydrochloride until the molar concentration of the hydrochloride in the pure water is 1.70mol/L, and adding the hydrochloride into an alkali chamber storage tank of a bipolar membrane electrodialysis device;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 220V voltage and 125A current to the membrane stack, controlling the temperature of the membrane stack to be 30-40 ℃, changing water for 1 time when the conductivity of hydrochloric acid in an acid chamber storage tank is 396ms/cm, switching off power when the conductivity of an alkali chamber is reduced to 0.3ms/cm, and operating for 10 hours;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 5-7 h, crystallizing at 10-20 ℃ for 2-3 h, filtering and drying to obtain 273g of product, wherein the content of cysteine chloride ions is 50 ppm-200 ppm, the removal rate of the chloride ions is 99.9 percent, and the yield of the product is 52.0 percent.
Comparative example 1
1000g of L-cysteine hydrochloride raw material is weighed, 1500mL of pure water is added for dissolution, and the mixture is heated to 60 +/-5 ℃ to fully dissolve the material. Filtering the solution through a fine filter of 10 mu m, slowly dripping 30 percent by mass of sodium hydroxide solution into the filtrate after the filtering is finished, controlling the temperature and adjusting the speed of adding alkali liquor during the process of adding the alkali liquor, controlling the temperature of the reaction liquor at 80-90 ℃ and stopping adding the alkali liquor until the pH value is 3.5-5.0. Slowly cooling to below 5 ℃ by using circulating water, and stirring until the materials are completely crystallized. Leaching with pure water during suction filtration, and drying to obtain 500g of product, wherein the content of chloride ions in the product is 1000-2000 ppm, and the yield of the product is 50%.
Comparative example 2
1000g of L-cysteine hydrochloride raw material is weighed, 1500mL of pure water is added for dissolution, and the mixture is heated to 60 +/-5 ℃ to fully dissolve the material. Filtering the solution through a 10-micron fine filter, slowly dropwise adding 30% sodium hydroxide solution into the filtrate after filtering, controlling the temperature and adjusting the alkali solution adding speed during the alkali solution adding process, controlling the temperature of the reaction solution at 80-90 ℃, and stopping adding the alkali solution until the pH value is 3.5-5.0. Slowly cooling to below 5 ℃ by using circulating water, and stirring until the material is completely crystallized. Leaching with ethanol during suction filtration, and drying to obtain 430g of product with cysteine chloride ion content of 400ppm and product yield of 43%.
Comparative example 3: see CN201410258617 for examples
Mixing 1000kg of L-cystine and hydrochloric acid according to a certain proportion, adjusting the pH value to be between 0.9 and 1.1, heating to about 60 ℃, adding activated carbon for decolorization, sending a decolorized solution into an electrolytic tank for electrolysis to obtain an L-cysteine hydrochloride acid solution, slowly adding a sodium hydroxide solution with a certain concentration into the L-cysteine hydrochloride acid solution for neutralization reaction, controlling the reaction temperature to be between 80 and 90 ℃, regulating and controlling the pH value of the mixed solution to be between 3.5 and 5.0, then slowly cooling for crystallization, carrying out suction filtration and drying to obtain 365g of an L-cysteine product, wherein the content of cysteine chloride ions is 400 to 2000ppm, and the product yield is 41%.
Comparative example 4
1.5L of 1% dilute sulfuric acid is prepared and added into an electrodialysis equipment polar liquid storage tank; adding pure water into the storage tank of the acid chamber; weighing 1000g of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the hydrochloride until the molar concentration of the hydrochloride in the pure water is 1.73mol/L, and adding the hydrochloride into an alkali chamber storage tank of electrodialysis equipment;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 24V voltage and 21A current to the membrane stack, changing water for 1 time when the conductivity of acid water in the acid chamber storage tank is 190ms/cm, changing water for 3 times at the later stage, switching off power when the conductivity of the alkali chamber is reduced to 20.9ms/cm, and running for 68min;
taking out the feed liquid, decompressing and concentrating at 80 ℃ for 0.5-1h, crystallizing at 10-20 ℃ for 0.5h, and performing suction filtration and drying to obtain 155g of product, wherein the content of cysteine chloride ion is 1000 ppm-2000 ppm, the chloride ion removal rate is 85%, and the product yield is 26%.
Comparative example 5
1.5L of 1 percent dilute sulfuric acid is prepared and added into an electrodialytic equipment polar liquid storage tank; adding pure water into the storage tank of the acid chamber; weighing 1000g of L-cysteine monohydrate hydrochloride, adding pure water to dissolve the hydrochloride until the molar concentration of the hydrochloride in the pure water is 1.70mol/L, and adding the hydrochloride into an alkali chamber storage tank of electrodialysis equipment;
switching on a power supply, starting each chamber driving pump to start a circulation loop, applying 24V voltage and 21A current to the membrane stack, changing water for 1 time when the conductivity of acid water in the acid chamber storage tank is 190ms/cm, changing water for 3 times at the later stage, and switching off when the conductivity of the alkali chamber is reduced to 20.3 ms/cm;
the operation is carried out for 80min, the feed liquid is taken out, the reduced pressure concentration is carried out for 0.5 to 1h at the temperature of 80 ℃, the crystallization is carried out for 0.5h at the low temperature of 10 to 20 ℃, the suction filtration and the drying are carried out, and 155g of product is obtained, the content of cysteine chloride ion is 3000ppm to 5000ppm, the removal rate of the raw material chloride ion is 76 percent, and the product yield is 43 percent.
Effect example 1
The following standard test methods and procedures for the products described in the present embodiment were performed with reference to the specifications of the japanese pharmacopoeia. The specific test results are shown in table 1 below.
TABLE 1 examination results of products prepared in examples and comparative examples
Table 2 shows the detection standards of L-cysteine products in the Japanese AJI97 (see also, qiaozhu in the amino acid industry) and the Japanese pharmacopoeia, respectively. By comparing the inspection results of the product of the embodiment with the inspection results of the product of the embodiment, the important indexes of the product obtained by the preparation method of the invention can reach the standard requirements of the enterprise and the Japanese pharmacopoeia.
TABLE 2 AJI97 and L-cysteine product assay Standard Table in Japanese pharmacopoeia
Remarking: "- -" indicates that this standard tool book is not mentioned.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of cysteine is characterized by comprising the following steps:
1) Adding an electrode solution into an electrode solution storage tank of a bipolar membrane electrodialysis device, adding pure water into an acid chamber storage tank, and adding a cysteine hydrochloride aqueous solution into an alkali chamber storage tank;
2) Switching on a power supply, starting each chamber driving pump to start a circulation loop, applying voltage and current to the membrane stack, changing water when the conductivity in the acid chamber storage tank is 200-396 ms/cm, switching off the power when the conductivity in the alkali chamber is reduced to 0.3-30 ms/cm, and taking out the feed liquid in the alkali chamber;
3) Carrying out post-treatment on the alkali chamber feed liquid;
wherein n is selected from 0 or 1.
2. The method according to claim 1, wherein the cysteine is L-cysteine, D-cysteine, or a mixture thereof.
3. The production process according to claim 1, wherein, in the step 1),
the polar aqueous solution is selected from one or more of dilute sulfuric acid, dilute nitric acid, sodium hydroxide aqueous solution and dilute hydrochloric acid; and/or the presence of a gas in the gas,
the mass fraction of the polar aqueous solution is 1-2%;
and/or the presence of a gas in the gas,
the dosage of the polar aqueous solution is 1-3L, or 1.5-2L, or 150L;
and/or the presence of a gas in the gas,
the mol concentration of the cysteine hydrochloride aqueous solution is 1.5-1.7 mol/L, or 1.63-1.68 mol/L, or 1.65mol/L.
4. The method of claim 3, wherein in step 1), the aqueous solution is dilute sulfuric acid, dilute nitric acid, or dilute hydrochloric acid.
5. The production method according to claim 1, wherein, in the step 2),
the voltage is 24-28V or 220V;
and/or the presence of a gas in the gas,
the current is 21-25A or 125A;
and/or the presence of a gas in the atmosphere,
the conductivity in the acid chamber storage tank during water change is 200-390 ms/cm or 300ms/cm;
and/or the presence of a gas in the gas,
the water changing times are 1-6 times, 1-4 times or 1-2 times;
and/or the presence of a gas in the atmosphere,
the power is cut off when the conductivity in the alkali chamber is reduced to 0.3-10 ms/cm, or the power is cut off when the conductivity in the alkali chamber is reduced to 0.3-0.5 ms/cm;
and/or the presence of a gas in the atmosphere,
the running time is 30-80 min, or 36-65 min, or 47-55 min, or 9-10 h;
and/or the presence of a gas in the atmosphere,
the temperature of the film stack is 30-40 ℃.
6. The preparation method according to claim 1, wherein in the step 3), the post-treatment comprises concentration under reduced pressure, low-temperature crystallization, suction filtration and drying.
7. The process according to claim 6, wherein the concentration under reduced pressure is carried out at 80 ℃ for 0.5 to 1 hour or at 80 ℃ for 5 to 7 hours.
8. The method according to claim 6, wherein the low-temperature crystallization time and the low-temperature crystallization temperature are 0.5 hour at 10 to 20 ℃ or 2 to 3 hours at 10 to 20 ℃.
9. The preparation method of claim 1, wherein the bipolar membrane electrodialysis device comprises a membrane stack and a cathode plate, the electrodialysis membrane stack comprises a bipolar membrane, an anion exchange membrane and a cation exchange membrane which are sequentially stacked in a certain order; the cation exchange membrane faces the polar plate, and a polar chamber is formed between the polar plate and the cation exchange membrane; an acid chamber is formed between the anion exchange membrane and the cation exchange membrane, and an alkali chamber is formed between the anion exchange membrane and the bipolar membrane; the polar chamber is communicated with a polar liquid storage tank, the acid chamber and the alkali chamber are respectively communicated with an acid liquid storage tank and an alkali liquid storage tank, and the indoor solutions and the storage tanks are respectively driven by a driving pump to form respective circulation loops; the polar chamber, the acid chamber and the alkali chamber are all provided with conductivity meters, and the conductivity change of the solution in each chamber is monitored at any time.
10. The production method according to claim 9, wherein the bipolar membrane and the anion-exchange membrane are repeatedly stacked 4 to 50 times, or 10 to 50 times.
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